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WO2008014273A1 - Mélange d'élastomère contenant des polycarbonates et des copolyétheresters dérivés de téréphtalate de polyéthylène, procédé de fabrication, et articles formés à partir de ceux-ci - Google Patents

Mélange d'élastomère contenant des polycarbonates et des copolyétheresters dérivés de téréphtalate de polyéthylène, procédé de fabrication, et articles formés à partir de ceux-ci Download PDF

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Publication number
WO2008014273A1
WO2008014273A1 PCT/US2007/074242 US2007074242W WO2008014273A1 WO 2008014273 A1 WO2008014273 A1 WO 2008014273A1 US 2007074242 W US2007074242 W US 2007074242W WO 2008014273 A1 WO2008014273 A1 WO 2008014273A1
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WO
WIPO (PCT)
Prior art keywords
composition
polyethylene terephthalate
group
derived
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2007/074242
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English (en)
Inventor
Peter H. Vollenberg
Dhaval Shah
Kenneth F. Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
General Electric Co
Original Assignee
SABIC Innovative Plastics IP BV
General Electric Co
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Application filed by SABIC Innovative Plastics IP BV, General Electric Co filed Critical SABIC Innovative Plastics IP BV
Priority to EP07799784A priority Critical patent/EP2044151A1/fr
Publication of WO2008014273A1 publication Critical patent/WO2008014273A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • This disclosure relates to compositions and methods of preparation of blends containing polyesters and copolyetherester elastomers, methods for their manufacture, and articles thereof.
  • the elastomer blends are derived from polyesters, in particular polyethylene terephthalate.
  • PET Polyethylene terephthalate
  • PET is a polyester of terephthalic acid and ethylene glycol that can be obtained by the polycondensation of dimethyl terephthalate with ethylene glycol, and also terephthalic acid with ethylene glycol or ethylene oxide.
  • PET exists both as an amorphous (transparent) and as a semi-crystalline (opaque and white) thermoplastic material. Generally, it has useful chemical resistance to mineral oils, solvents, and acids but not to bases.
  • Semi- crystalline PET has good strength, ductility, stiffness, and hardness. Amorphous PET has better ductility but less stiffness and hardness. PET is used to make bottles for soft drinks and other household and consumer products. Generally, PET has many uses and several large markets. For this reason, the volume of PET manufactured is large and growing.
  • Copolyetheresters are a special class of elastomeric materials. These materials exhibit thermoplastic processability on conventional molding equipment and exhibit the elasticity and resistance to impact and flex-fatigue of conventional cured rubbers. The combination of properties is obtained due to the result of the phase separation between the amorphous polyether segments (polyether blocks) and the crystalline polyester segments (polyester blocks) of the copolymer molecule. Because the immiscible segments are copolymerized into a single macromolecular backbone the necessary phase separation that occurs results in discrete domains with dimensions on the order of magnitude of the polymer chain.
  • the polyether forms soft, amorphous domains that are physically crosslinked by the 'knots' of crystalline, polyester domains. That is, the amorphous soft blocks provide the elastomeric properties of flexibility and low temperature impact while the presence of the crystalline hard blocks result in discrete melting points, heat and chemical resistance, and mechanical strength. These materials are also commonly characterized by a lower temperature brittleness point than conventional rubbers, resilience, low creep, and very good resistance to oils, fuels, solvents, and chemicals.
  • molding compositions based on conventional copolyetheresters derived from PET are useful to many customers, these molding compositions can lack the ability to strike certain property balances, for example the combination of low temperature (-4O 0 C) ductility with a tensile modulus of about 1000 MPa, and/or the combination of optical transparency with good flexibility.
  • blends of polycarbonate or polycarbonate copolymers with copolyetheresters based on post-consumer PET create the ability and flexibility to create desired property balances for targeted applications.
  • GB 1500577 discloses the treatment of scrap PET with an alkylene glycol in an amount equal to from 0.1 to 5 times the weight of the scrap PET. In a preferred embodiment, GB 1500577 discloses that these materials are heated at 200 to 250 0 C to reflux the glycol for a period of about 8 hours or until the solution becomes clear.
  • the first portion of the glycolization step is preferably carried out at atmospheric pressure and the final portion preferably is carried out at a pressure less than 0.5 mm Hg.
  • Example 4 of U.S. Patent No. 3,701,755 discloses that "12.17 parts of bis(2-hydroxy ethyl) terephthalate, 20.0 parts of poly(tetramethylene oxide)glycol (PTMG) with a molecular weight of 1800 and 0.014 part[s] of zinc[ ] acetate were charged into a reaction vessel at 200° C.
  • PTMG poly(tetramethylene oxide)glycol
  • EP 1437377 discloses a process that involves a depolymerization reaction of used PET bottles with ethylene glycol, recovering dimethyl terephthalate (DMT) by ester interchange reaction with methanol, obtaining terephthalic acid by hydrolysis of the recovered DMT, and manufacturing a PET polymer that can be used for manufacturing PET bottles again by using the terephthalic acid.
  • DMT dimethyl terephthalate
  • terephthalic acid by hydrolysis of the recovered DMT
  • manufacturing a PET polymer that can be used for manufacturing PET bottles again by using the terephthalic acid do not address the need to make copolyetheresters that have suitable commercial properties from scrap PET, e.g., copolyetheresters having properties comparable to PBT-based copolyetheresters.
  • composition comprising: from 10 to 90 weight percent of a copolyetherester elastomer comprising: a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate, polyethylene terephthalate copolymers, and combinations thereof; and that contains at least one residue derived from the polyethylene terephthalate component; and a polyalkylene oxide copolymer block that is derived from the polyethylene terephthalate component and a polyalkylene oxide glycol, and that contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component; from 10 to 90 weight percent of a polycarbonate; and from 0 to 60 weight percent of a polyester.
  • a copolyetherester elastomer comprising: a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component
  • Another embodiment is a composition comprising from 50 to 55 weight percent of a copolyetherester elastomer comprising: a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate, polyethylene terephthalate copolymers, and combinations thereof; and that contains at least one residue derived from the polyethylene terephthalate component; and a polyalkylene oxide copolymer block that is derived from the polyethylene terephthalate component and a polyalkylene oxide glycol, and that contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component; and from 45 to 50 weight percent of a polycarbonate copolymer comprising units derived from l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane; wherein an article molded from the composition having a thickness of 3.2 mm has a transmission of
  • Another embodiment is a composition comprising from 20 to 30 weight percent of a copolyetherester elastomer comprising: a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate, polyethylene terephthalate copolymers, and combinations thereof; and that contains at least one residue derived from the polyethylene terephthalate component; and a polyalkylene oxide copolymer block that is derived from the polyethylene terephthalate component and a polyalkylene oxide glycol, and that contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component; from 20 to 35 weight percent of a polycarbonate copolymer comprising units derived from l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane; and from 40 to 55 weight percent of poly(l,4-cyclohexylenedimethylene-l
  • a method of manufacture of the above-described compositions comprises combining the components of the compositions; and extruding the blended compositions.
  • a method of manufacture of an article comprises molding or extruding the above-described compositions.
  • Another embodiment is a method of preparing the copolyetherester elastomer, comprising combining a polyethylene terephthalate component, 1 ,4-butane diol, and a catalyst in a reactor in a liquid phase under agitation; depolymerizing the polyethylene terephthalate component by reacting the polyethylene terephthalate and the 1 ,4-butane diol under at least atmospheric pressure and an inert atmosphere, under conditions sufficient to depolymerize the polyethylene component into a molten mixture containing oligomers, 1 ,4-butane diol, ethylene glycol, and mixtures thereof, while refluxing the 1 ,4-butane diol back into the reactor; and agitating the molten mixture under subatmospheric pressure and removing excess diol, ethylene glycol, and tetrahydrofuran; and adding the polyalkylene oxide during the process in an amount and under conditions that are sufficient to form thermoplastic cop
  • thermoplastic copolyetherester elastomer comprises depolymerizing a polyethylene terephthalate component by agitating the polyethylene terephthalate component with a member selected from the group consisting of ethylene glycol, 1,3-propane diol, and combinations thereof, in a reactor under at least atmospheric pressure in the presence if a catalyst component under conditions sufficient to depolymerize the polyethylene terephthalate component into a first molten mixture that comprises components selected from the group consisting of oligomers containing ethylene terephthalate moieties, oligomers containing trimethylene terephthalate moieties, ethylene glycol, propylene glycol, and combinations thereof; adding 1 ,4-butane diol to the first molten mixture in a reactor in the presence of a catalyst component, under conditions sufficient to form a second molten mixture containing a component selected from the group consisting of oligomers containing ethylene
  • the invention is based on the discovery that it is now possible to make blends of polycarbonates and copolyetheresters derived from scrap polyethylene terephthalate that exhibit outstanding performance properties.
  • the copolyetheresters of the invention contain residues derived from polyethylene terephthalate, e.g., ethylene glycol, isophthalic acid, and diethylene glycol groups. Despite this, the copolyetheresters impart excellent performance properties and can be used in many applications.
  • terephthalic acid group in a composition refers to a divalent 1,4-benzene radical (-1,4-C 6 H 4 -) remaining after removal of the carboxylic groups from terephthalic acid-.
  • isophthalic acid group R" refers to a divalent 1,3- benzene radical (-1,3-C 6 H 4 -) remaining after removal of the carboxylic groups from isophthalic acid.
  • butane diol group refers to a divalent butylene radical (-C 4 H 8 -) remaining after removal of hydroxyl groups from butane diol.
  • ethylene glycol group refers to a divalent ethylene radical (-C 2 H 4 -) remaining after removal of hydroxyl groups from ethylene glycol.
  • isophthalic acid group means the group having the formula -OC(O)C 6 H 4 C(O)-
  • terephthalic acid group(s) means the group having the formula -OC(O)C 6 H 4 C(O)-
  • diethylene glycol group means the group having -OC 2 H 4 -O-C 2 H 4 -
  • butane diol group(s) means the group having the formula -OC 4 Hg-
  • ethylene glycol groups(s) means the group having formula -OC 2 H 4 -.
  • translucent have the following meanings.
  • An article having a transmission of greater than or equal to 60% is classified as transparent, an article having a transmission of greater than or equal to 35% and less than 60% is classified as translucent, and an article having a transmission of less than 35% is classified as opaque.
  • Haze and total luminous transmittance (%) are each measured in accordance with ASTM D 1003-00. The foregoing classification is based on samples having a thickness of 3.2 mm.
  • the invention relates to a composition
  • a composition comprising from 10 to 90 weight percent of a thermoplastic copolyetherester elastomer derived from, in particular, post-consumer polyethylene terephthalate.
  • the random copolyetherester contains a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers, or a combination thereof; and contains at least one residue derived from the polyethylene terephthalate component; and a polyalkylene oxide copolymer block that is derived from a polyethylene terephthalate component and polyalkylene oxide glycol, and contains polyalkylene oxide and at least one residue derived from the polyethylene terephthalate component.
  • the composition further comprises from 10 to 90 weight percent of a polycarbonate (which as used herein includes a polycarbonate copolymer), in particular polycarbonate copolymers comprising cyclohexyl groups and/or siloxane groups.
  • the compositions further comprise from 0 to 60 weight percent of a polyester, in particular a poly(l,4- cyclohexylenedimethylene-l,4-cyclohexane dicarboxylate).
  • Articles molded from the compositions having a thickness of 3.2 mm have good transparency, e.g., a transmission of 35% or higher.
  • the invention relates to a composition
  • a composition comprising:
  • a modified, random polybutylene terephthalate copolymer block that is derived from a polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and combinations thereof; and contains at least one residue derived from the polyethylene terephthalate component;
  • the residue derived from the polyethylene terephthalate component can be selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, cobalt- containing compounds, antimony-containing compounds, germanium-containing compounds, tin containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1 ,4-cyclohexane dimethanol isomers, the cis isomer of 1,3- cyclohexane dimethanol, the cis isomer of 1 ,4-cyclohexane dimethanol, the trans isomer of 1,3-cyclohexane dimethanol, the trans isomer of 1 ,4-cyclohexane dimethanol, alkali salts, alkaline salts, naphthalene dicarboxylic acids, 1,3-propane diol groups, and combinations thereof.
  • the residue can include various combinations.
  • the residue derived from the polyethylene terephthalate component comprises mixtures of ethylene glycol and diethylene glycol.
  • Such mixtures can include additional materials, such as isophthalic acid.
  • Such mixtures can also include the cis isomer of 1,3-cyclohexane dimethanol, cis isomer of 1 ,4-cyclohexane dimethanol, trans isomer of 1,3-cyclohexane dimethanol, trans isomer of 1 ,4-cyclohexane dimethanol and combinations thereof.
  • the residue derived from the polyethylene terephthalate component can selected from the group of cis isomer of 1,3-cyclohexane dimethanol, cis isomer of 1 ,4-cyclohexane dimethanol, the trans isomer of 1,3-cyclohexane dimethanol, trans isomer of 1,4- cyclohexane dimethanol and combinations thereof.
  • the residue derived from the polyethylene terephthalate component can be selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, cis isomer of 1,3-cyclohexane dimethanol, trans isomer of 1,3- cyclohexane dimethanol, cis isomer of 1 ,4-cyclohexane dimethanol, trans isomer of 1 ,4-cyclohexane dimethanol, and combinations thereof.
  • the residue derived from the polyethylene terephthalate component comprises mixtures of ethylene glycol, diethylene glycol, and cobalt-containing compounds. As above, in such mixtures, the at least one residue derived from the polyethylene terephthalate component further comprises isophthalic acid groups.
  • the molar amounts of the residue derived from the polyethylene terephthalate component can vary.
  • the residue derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups, and cyclohexane dimethanol groups, and is in an amount ranging from 0.1 to 10 mole %, based on 100 mole % of glycol in the copolyetherester.
  • the residue derived from the polyethylene terephthalate component further comprises isophthalic acid groups in an amount ranging from 0 to 10 mole%, based on 100 mole % of acid functionality in the copolyetherester terephthalate copolymer.
  • the total amount of materials of the polyethylene terephthalate residue can vary. For instance, sometimes, mixtures can be in an amount ranging from 1.8 to 2.5 wt%, or from 0.5 to 2 wt%, or from 1 to 4 wt%.
  • the diethylene glycol group can be present in an amount ranging from 0.1 to 10 mole %, based on 100 mole % of glycol in the copolyetherester.
  • the isophthalic acid group can be present in an amount ranging from 0.1 to 10 mole %, based on 100 mole % of acid in the copolyetherester.
  • the amount of the random polybutylene terephthalate copolymer block in the copolyetherester can vary. In one embodiment, the amount of the random polybutylene terephthalate copolymer ranges from 5 to 95, specifically from 20 to 80 wt%, based on 100 wt% of the total copolyetherester.
  • the recycle PET component from which the modified polybutylene terephthalate random copolymer is derived can be in any form that can be used according to the invention.
  • the PET component includes recycle (scrap) PET from any source.
  • the PET can be post-consumer PET, and/or scrap PET from manufacturing processes of the PET itself or articles comprising the PET.
  • the PET component comprises post-consumer PET.
  • the PET can be in flake, powder/chip, film, or pellet form. Before use, the PET is generally processed to remove impurities such as paper, adhesives, polypropylene polyvinyl chloride (PVC), nylon, polylactic acid, and other contaminants.
  • PVC polypropylene polyvinyl chloride
  • the PET component can include PET that is not waste in flake, chip, or pellet form. As such, PET that would ordinarily be deposited in landfills can now be used productively and effectively.
  • the PET component can also include other types of polyesters.
  • the PET component can also include polyester copolymers.
  • terephthalates such as virgin polyethylene terephthalate, polycyclohexane terephthalate, copolyesters of terephthalate esters with comonomers derived from cyclohexyl dimethanol and ethylene glycol, copolyesters of terephthalic acid with comonomers containing cyclohexyl dimethanol and ethylene glycol, polybutylene terephthalate, poly-xylylene terephthalate, polydianol terephthalates, polybutylene terephthalate, polytrimethylene terephthalate, polyester naphthalates, and combinations thereof.
  • the polyalkylene oxide glycol can be selected from the group consisting of polyethylene oxide glycols, polypropylene oxide glycols, polybutylene oxide glycols, and combinations thereof.
  • the polyalkylene oxide can be selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and combinations thereof. The amounts will vary, depending on the process conditions, customer needs, and the like.
  • the process for making the copolyetheresters in the blends can vary. In one embodiment, for instance, the process involves the steps of:
  • the temperatures used in such a variation can vary.
  • the polyethylene terephthalate can be depolymerized in various temperatures, e.g., a temperature ranging from 180 to 260 0 C.
  • the temperature of the molten mixture is increased to a temperature ranging from 240 to 27O 0 C.
  • the polyalkylene oxide glycol can be added at various stages of the process. In one embodiment, the polyalkylene oxide glycol is added during the depolymerization of the polyethylene terephthalate component. In another embodiment, the polyalkylene oxide glycol is added during the agitation of the molten mixture under subatmospheric pressure.
  • the process contains an advantageous version in which one or more diols used in the process, for example, 1 ,4-butane diol, polyalkylene oxide glycol, 1,3-propane diol, and combinations thereof are derived from biomass, e.g., a grain such as corn or wheat, a cellulosic material, or a combination thereof.
  • biomass e.g., a grain such as corn or wheat, a cellulosic material, or a combination thereof.
  • biomass means living or dead biological matter that can be directly or subsequently converted to useful chemical substances that are ordinarily derived from non-renewable hydrocarbon sources.
  • Biomass can include cellulosic materials, grains, starches derived from grains, fatty acids, plant based oils, as well as derivatives from these biomass examples.
  • useful chemical substances include and are not limited to diols; diacids; monomers used to make diols or acids, (e.g., succinic acid), monomers used to make polymers; and the like.
  • Biomass-based diols can be obtained from several sources. For instance, the following process can be used to obtain biomass-based 1,4-butane diol.
  • Agriculture based biomass such as corn, can be converted into succinic acid by a fermentation process that also consumes carbon dioxide.
  • succinic acid is commercially available from several sources such as from Diversified Natural Products Inc. under the trade name "BioAmberTM.”
  • This succinic acid can be easily converted into 1,4-butane diol by processes described in several prior art references, such as in U.S. Patent No. 4,096,156.
  • Biomass-derived 1,4-butane diol can also be converted to tetrahydrofuran, and further converted to polytetrahydrofuran, also known as polybutylene oxide glycol.
  • Another process that describes converting succinic acid into 1,4-butane diol is sort forth in Life Cycles Engineering Guidelines, by Smith et al., as described in EPA publication EPA/600/R-1/101 (2001).
  • copolyetheresters can be made by:
  • step (d) adding the polyalkylene oxide glycol during the process in an amount and under conditions that are sufficient to form the copolyetherester, and oligomers containing trimethylene terephthalate moieties, propylene glycol, and ethylene glycol are removed during formation of the copolyetherester.
  • the embodiment can also include variations. For instance, temperatures used during the process can vary.
  • the polyethylene terephthalate component for instance, can be depolymerized at a temperature ranging from 190 to 250 0 C, under an inert atmosphere.
  • Step (b) of this embodiment (where 1 ,4-butane diol is added to the first molten mixture) can be conducted at a temperature ranging from 190 to 240 0 C.
  • step (c) where the second molten mixture is subjected to subatmospheric conditions and agitation sufficient to form the copolyetherester), the temperature can be increased to a temperature ranging from 240 to 26O 0 C.
  • the polyalkylene oxide glycol can be added at different stages of the process. In one embodiment, the polyalkylene oxide glycol is added during the depolymerization of the polyethylene terephthalate component. In another embodiment, the polyalkylene oxide glycol is added during the agitation of the first molten mixture. In another embodiment, the polyalkylene oxide glycol is added during the agitation of the second molten mixture.
  • the amounts of the polyalkylene oxide can vary. In one embodiment, the polyalkylene oxide is present in an amount ranging from 5 to 95 wt%, specifically 20 to 80 wt% polyalkylene oxide, based on the total weight of the copolyetherester.
  • the 1,4-butane diol, polyalkylene oxide, or a combination thereof in the foregoing embodiments can be derived from biomass.
  • the biomass is a grain selected from the group consisting of a grain such as corn or wheat, cellulosic material, and a combination thereof.
  • the polyalkylene oxide can be selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and combinations thereof. The amounts will vary, depending on the process conditions, customer needs, and the like.
  • a polybutylene oxide glycol is used to provide the polyoxyalkylene groups, i.e., the polyalkylene oxide copolymer block comprises poly(l,4-butylene oxide).
  • the polybutylene oxide glycol can have a number-average molecular weight of 100 to 5000 Daltons, or more specifically, 150 to 4,000, or even more specifically, 200 to 3,000 Daltons.
  • a combination of long and short chain polybutylene oxide glycols is used, for example a polybutylene oxide glycol component having a number average molecular weight of 100 to 5000 Daltons, and another polybutylene oxide glycol component having a molecular weight of less than 2500.
  • a specific polybutylene oxide glycol for use in the foregoing embodiments is poly(l,4-butylene oxide) glycol.
  • copolyetheresters used in the blends can comprise the following:
  • G is the divalent polyalkylene oxide radical remaining after removal of the terminal hydroxyl groups from a poly(butylene oxide) glycol having a number- average molecular weight of 100 to 5000 Daltons; and R' is the divalent terephthalic radical remaining after removal of the carboxyl groups from a terephthalic dicarboxylic acid; and R" is a divalent isophthalic radical remaining after removal of the carboxyl groups from an isophthalic dicarboxylic acid; and
  • D is the divalent butylene radical remaining after removal of the hydroxyl groups from butanediol having a molecular weight of less than 250; and R 5 and R" are as defined above; and wherein D 5 is a divalent ethylene radical after removal of hydroxyl groups of ethylene glycol or diethylene glycol.
  • the copolyetherester comprising polybutylene oxide groups further comprises terephthalic acid groups.
  • Such copolymers can have 25 to 65 wt%, more specifically 30 to 60 wt%, even more specifically 25 to 55 wt% of units derived from polybutylene oxide glycol or a chemical equivalent thereof, based on the weight of the copolymer.
  • a poly(butylene terephthalate-butylene oxide) copolymer can further comprise isophthalic acid in addition to terephthalic acid.
  • the poly(butylene terephthalate/isophthalate-o butylene oxide) copolymer comprises 0 to 40 mole % of units derived from isophthalic acid or a chemical equivalent thereof, based on the total number of isophthalate and terephthalate units.
  • the poly(butylene terephthalate/isophthalate-oxytetramethylene) copolymer can comprise less than 5 mole % of isophthalate units, specifically 0 to 5 mole % of isophthalate units, based on the total number of isophthalate and terephthalate units in the copolymer.
  • the poly(butylene terephthalate/isophthalate-oxytetramethylene) copolymer comprises greater than 5 mole % of isophthalate units, specifically 5 to 40 mole %, based on the total number of isophthalate and terephthalate units in the copolymer.
  • the copolyetheresters made from the recycle PET can be characterized by the glass transition temperature (Tg) of the soft block and the melting temperature (Tm) of the hard block.
  • Tg glass transition temperature
  • Tm melting temperature
  • the Tg of the soft block can be -25 to -85°C, specifically -45 to -65°C
  • Tm of the hard block can be 120 to 200 0 C, specifically 150 to 195°C.
  • the polycarbonate component can be any polycarbonate, which when combined with the copolyetheresters, forms a blend.
  • polycarbonate and polycarbonate resin mean compositions having repeating structural carbonate units of the formula (1):
  • each R 1 is an aromatic organic radical, for example a radical of the formula (2):
  • each of A 1 and A 2 is a monocyclic divalent aryl radical and Y 1 is a bridging radical having one or two atoms that separate A 1 from A 2 .
  • one atom separates A 1 from A 2 .
  • radicals of this type are -O-, -S-, -S(O)-, -S(O 2 )-, -C(O)-, methylene, cyclohexyl- methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene.
  • the bridging radical Y 1 can be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.
  • aliphatic refers to a hydrocarbon radical having a valence of at least one comprising a linear or branched array of carbon atoms which is not cyclic; "aromatic” refers to a radical having a valence of at least one comprising at least one aromatic group; “cycloaliphatic” refers to a radical having a valence of at least one comprising an array of carbon atoms which is cyclic but not aromatic; "alkyl” refers to a straight or branched chain monovalent hydrocarbon radical; “alkylene” refers to a straight or branched chain divalent hydrocarbon radical; “alkylidene” refers to a straight or branched chain divalent hydrocarbon radical, with both valences on a single common carbon atom; “alkenyl” refers to a straight or branched chain monovalent hydrocarbon radical having at least two carbons joined by a carbon-carbon double bond; “cycloalkyl” refer
  • R a and R b each represent a halogen atom or a monovalent hydrocarbon group and can be the same or different; p and q are each independently integers of 0 to 4; and X a represents one of the groups of formula (5):
  • R c and R d each independently represent a hydrogen atom or a monovalent linear or cyclic hydrocarbon group and R e is a divalent hydrocarbon group.
  • X a is cyclohexylidene.
  • a specific example wherein X a is a substituted cycloalkylidene is the cyclohexylidene-bridged, alkyl-substituted bisphenol of formula (6)
  • R a and R are each independently C 1-12 alkyl, R g is C 1-12 alkyl or halogen, r and s are each independently 1 to 4, and t is 0 to 10.
  • at least one of each of R a and R b are disposed Meta to the cyclohexylidene bridging group.
  • the substituents R a , R b , and R g may, when comprising an appropriate number of carbon atoms, be straight chain, cyclic, bicyclic, branched, saturated, or unsaturated.
  • R a and R b are each independently C 1-4 alkyl, R g is Ci_ 3 alkyl, r and s are each 1 to 2, and t is 0 to 5, specifically 0.
  • R a , R b and R g are each methyl, r and s are each 1, and t is 0 or 3.
  • the cyclohexylidene-bridged bisphenol can be the reaction product of two moles of o- cresol with one mole of cyclohexanone.
  • the cyclohexylidene-bridged bisphenol is the reaction product of two moles of a cresol with one mole of a hydrogenated isophorone (e.g., l,l,3-trimethyl-3-cyclohexane-5- one).
  • a hydrogenated isophorone e.g., l,l,3-trimethyl-3-cyclohexane-5- one.
  • Such cyclohexane-containing bisphenols for example the reaction product of two moles of a phenol with one mole of a hydrogenated isophorone, are useful for making polycarbonate polymers with high glass transition temperatures and high heat distortion temperatures.
  • suitable dihydroxy compounds include the following: resorcinol, 4-bromoresorcinol, hydroquinone, 4,4'- dihydroxybiphenyl, 1 ,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4- hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4- hydroxyphenyl)- 1 -naphthylmethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 1 , 1 -bis(4- hydroxyphenyl)- 1 -phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl) propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromo-phenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentan
  • bisphenol compounds represented by formula (3) include l,l-bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (hereinafter "bisphenol A” or "BPA”), 2,2- bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4- hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l- methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4- hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP), and l,l-bis(4-hydroxy-3-methylphenyl)cycl
  • Combinations comprising at least one of the foregoing dihydroxy compounds can also be used.
  • copolymer can be used, comprising a mixture of units derived from bisphenol A and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane.
  • Branched polycarbonates are also useful, as well as blends of a linear polycarbonate and a branched polycarbonate.
  • the branched polycarbonates can be prepared by adding a branching agent during polymerization.
  • branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
  • trimellitic acid trimellitic anhydride
  • trimellitic trichloride tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris- phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1- bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • the branching agents can be added at a level of 0.05 to 2.0 wt% of the polycarbonate. All types of polycarbonate end groups are contemplated as being useful in the polycarbonate, provided that such end groups do not significantly affect desired properties of the thermoplastic compositions.
  • the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene.
  • the polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25 0 C, of 0.3 to 1.5 deciliters per gram (dl/g), specifically 0.45 to 1.0 dl/g.
  • the polycarbonates can have a weight average molecular weight (Mw) of 10,000 to 100,000, as measured by gel permeation chromatography (GPC) using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards.
  • Mw weight average molecular weight
  • Polycarbonates and “polycarbonate resin” as used herein can include copolymers comprising carbonate chain units.
  • a specific suitable copolymer is a polyester-polycarbonate, also known as a copolyester-polycarbonate and polyester- carbonate. Combinations of polycarbonates and polyester-polycarbonates can also be used.
  • a “combination” is inclusive of all mixtures, blends, alloys, reaction products, and the like.
  • Polyester-polycarbonates contain, in addition to recurring carbonate chain units of the formula (1), repeating units of formula (7):
  • D is a divalent radical derived from a dihydroxy compound, and can be, for example, a C 2-10 alkylene radical, a C6-20 alicyclic radical, a C6-20 aromatic radical or a polyoxyalkylene radical in which the alkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and T divalent radical derived from a dicarboxylic acid, and can be, for example, a C 2-10 alkylene radical, a C6-20 alicyclic radical, a C6-20 alkyl aromatic radical, or a C6-20 aromatic radical.
  • D is a C2-6 alkylene radical.
  • D is derived from an aromatic dihydroxy compound of formula (8):
  • each R is independently a halogen atom, a C 1-10 hydrocarbon group, or a C 1- 10 halogen substituted hydrocarbon group, and n is 0 to 4.
  • the halogen is usually bromine.
  • compounds that can be represented by the formula (7) include resorcinol, substituted resorcinol compounds such as 5 -methyl resorcinol, 5 -ethyl resorcinol, 5 -propyl resorcinol, 5 -butyl resorcinol, 5-t-butyl resorcinol, 5 -phenyl resorcinol, 5-cumyl resorcinol, 2,4,5, 6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2- methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone
  • polyesters examples include isophthalic or terephthalic acid, 1 ,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, and mixtures comprising at least one of the foregoing acids. Acids containing fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids.
  • Specific dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or mixtures thereof.
  • a specific dicarboxylic acid comprises a mixture of isophthalic acid and terephthalic acid wherein the weight ratio of terephthalic acid to isophthalic acid is 91 : 1 to 2:98.
  • D is a C 2 - 6 alkylene radical and T is p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic radical, or a mixture thereof.
  • This class of polyester includes the poly(alkylene terephthalates).
  • polyester-polycarbonates comprise carbonate units as described hereinabove.
  • Carbonate units of formula (1) can also be derived from aromatic dihydroxy compounds of formula (8), wherein specific carbonate units are resorcinol carbonate units.
  • the polyester unit of a polyester-polycarbonate can be derived from the reaction of a combination of isophthalic and terephthalic diacids (or derivatives thereof) with resorcinol, bisphenol A, or a combination comprising one or more of these, wherein the molar ratio of isophthalate units to terephthalate units is 91 :9 to 2:98, specifically 85:15 to 3:97, more specifically 80:20 to 5:95, and still more specifically 70:30 to 10:90.
  • the polycarbonate units can be derived from resorcinol and/or bisphenol A, in a molar ratio of resorcinol carbonate units to bisphenol A carbonate units of 0:100 to 99:1, and the molar ratio of the mixed isophthalate- terephthalate polyester units to the polycarbonate units in the polyester-polycarbonate can be 1 :99 to 99:1, specifically 5:95 to 90:10, more specifically 10:90 to 80:20. Where a blend of polyester-polycarbonate with polycarbonate is used, the weight ratio of polycarbonate to polyester-polycarbonate in the blend can be, respectively, 1 : 99 to 99:1, specifically 10:90 to 90:10.
  • the polyester-polycarbonates can have a weight-averaged molecular weight (Mw) of 1,500 to 100,000, specifically 1,700 to 50,000, and more specifically 2,000 to 40,000.
  • Mw weight-averaged molecular weight
  • Molecular weight determinations are performed using gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column, and calibrated to polycarbonate references. Samples are prepared at a concentration of about 1 mg/ml, and are eluted at a flow rate of about 1.0 ml/min.
  • Processes such as interfacial polymerization and melt polymerization can manufacture suitable polycarbonates.
  • reaction conditions for interfacial polymerization can vary, an exemplary process generally involves dissolving or dispersing a dihydric phenol reactant in aqueous caustic soda or potash, adding the resulting mixture to a suitable water-immiscible solvent medium, and contacting the reactants with a carbonate precursor in the presence of a suitable catalyst such as triethylamine or a phase transfer catalyst, under controlled pH conditions, e.g., 8 to 10.
  • a suitable catalyst such as triethylamine or a phase transfer catalyst
  • Suitable water immiscible solvents include methylene chloride, 1 ,2-dichloroethane, chlorobenzene, toluene, and the like.
  • Suitable carbonate precursors include, for example, a carbonyl halide such as carbonyl bromide or carbonyl chloride, or a haloformate such as a bishaloformates of a dihydric phenol (e.g., the bischloroformates of bisphenol A, hydroquinone, or the like) or a glycol (e.g., the bishaloformate of ethylene glycol, neopentyl glycol, polyethylene glycol, or the like).
  • a carbonyl halide such as carbonyl bromide or carbonyl chloride
  • a haloformate such as a bishaloformates of a dihydric phenol (e.g., the bischloroformates of bisphenol A, hydroquinone, or the
  • a chain stopper (also referred to as a capping agent) can be included during polymerization.
  • the chain- stopper limits molecular weight growth rate, and so controls molecular weight in the polycarbonate.
  • a chain-stopper can be at least one of mono-phenolic compounds, mono-carboxylic acid chlorides, and/or mono-chloroformates.
  • mono-phenolic compounds suitable as chain stoppers include monocyclic phenols, such as phenol, Ci_22 alkyl-substituted phenols, p-cumyl- phenol, p-tertiary-butyl phenol, hydroxy diphenyl; monoethers of diphenols, such as p-methoxyphenol.
  • Alkyl-substituted phenols include those with branched chain alkyl substituents having 8 to 9 carbon atoms.
  • a mono-phenolic UV absorber can be used as capping agent.
  • Such compounds include 4-substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2- hydroxyaryl)-l,3,5-triazines and their derivatives, and the like.
  • mono- phenolic chain-stoppers include phenol, p-cumylphenol, and/or resorcinol monobenzoate.
  • Mono-carboxylic acid chlorides can also be suitable as chain stoppers. These include monocyclic, mono-carboxylic acid chlorides such as benzoyl chloride, Ci_22 alkyl-substituted benzoyl chloride, toluoyl chloride, halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoyl chloride, 4-nadimidobenzoyl chloride, and mixtures thereof; polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydride chloride, and naphthoyl chloride; and mixtures of monocyclic and polycyclic mono-carboxylic acid chlorides.
  • monocyclic, mono-carboxylic acid chlorides such as benzoyl chloride, Ci_22 alkyl-substituted benzoyl chloride, toluoyl chloride, halogen-substituted benzoyl chloride, bromobenzoy
  • Chlorides of aliphatic monocarboxylic acids with up to 22 carbon atoms are suitable.
  • Functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, are also suitable.
  • mono-chloroformates including monocyclic, mono- chloroformates, such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumyl phenyl chloroformate, toluene chloroformate, and mixtures thereof.
  • the polyester-polycarbonates can be prepared by interfacial polymerization. Rather than utilizing the dicarboxylic acid per se, it is possible, and sometimes even preferred, to employ the reactive derivatives of the acid, such as the corresponding acid halides, in particular the acid dichlorides and the acid dibromides. Thus, for example instead of using isophthalic acid, terephthalic acid, or mixtures thereof, it is possible to employ isophthaloyl dichloride, terephthaloyl dichloride, and mixtures thereof.
  • phase transfer catalysts that can be used are catalysts of the formula (R 15 ) 4 Q X, wherein each R 15 is the same or different, and is a C 1-10 alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a Ci_8 alkoxy group or C 6 - I s aryloxy group.
  • Suitable phase transfer catalysts include, for example, [CH 3 (CH 2 )S] 4 NX, [CH 3 (CH 2 )S] 4 PX, [CH 3 (CH 2 ) 5 ] 4 NX, [CH 3 (CH 2 ) 6 ] 4 NX, [CH 3 (CH 2 ) 4 ] 4 NX, CH 3 [CH 3 (CH 2 ) 3 ] 3 NX, and CH 3 [CH 3 (CH 2 ) 2 ] 3 NX, wherein X is Cl " , Br " , a Ci_8 alkoxy group or a C 6-18 aryloxy group.
  • An effective amount of a phase transfer catalyst can be 0.1 to 10 wt% based on the weight of bisphenol in the phosgenation mixture. In another embodiment an effective amount of phase transfer catalyst can be 0.5 to 2 wt% based on the weight of bisphenol in the phosgenation mixture.
  • melt processes can be used to make the polycarbonates.
  • polycarbonates can be prepared by co- reacting, in a molten state, the dihydroxy reactant(s) and a diaryl carbonate ester, such as diphenyl carbonate, in the presence of a transesterification catalyst in a Banbury ® mixer, twin screw extruder, or the like to form a uniform dispersion. Volatile monohydric phenol is removed from the molten reactants by distillation and the polymer is isolated as a molten residue.
  • polyester-polycarbonates polysiloxane -polycarbonates, and combinations of these as described above
  • thermoplastic polymers for example combinations of polycarbonates and/or polycarbonate copolymers with polyesters.
  • the polycarbonate can also be a polysiloxane-polycarbonate copolymer, also referred to as a polysiloxane-polycarbonate.
  • the polysiloxane (also referred to herein as "polydiorganosiloxane") blocks of the copolymer comprise repeating siloxane units (also referred to herein as "diorganosiloxane units") of formula (9):
  • R is a C 1-13 monovalent organic radical.
  • R can independently be a C 1-13 alkyl group, C 1-13 alkoxy group, C 2-13 alkenyl group, C 2-13 alkenyloxy group, C3-6 cycloalkyl group, C3-6 cycloalkoxy group, C 6-14 aryl group, C 6-10 aryloxy group, C 7 _i 3 arylalkyl group, C 7 _i 3 arylalkoxy group, C 7 _i3 alkylaryl group, or C 7 _i 3 alkylaryloxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Combinations of the foregoing R groups can be used in the same copolymer.
  • E in formula (9) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and like considerations. Generally, E can have an average value of 2 to 1,000, specifically 2 to 500, and more specifically 5 to 100. In one embodiment, E has an average value of 10 to 75, and in still another embodiment, E has an average value of 40 to 60. Where E is of a lower value, e.g., less than 40, it can be desirable to use a relatively larger amount of the polycarbonate-polysiloxane copolymer. Conversely, where E is of a higher value, e.g., greater than 40, it can be necessary to use a relatively lower amount of the polycarbonate-polysiloxane copolymer.
  • a combination of a first and a second (or more) polysiloxane- polycarbonate copolymer can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.
  • polydiorganosiloxane blocks are provided by repeating structural units of formula (10):
  • each R can independently be the same or different, and is as defined above; and each Ar can independently be the same or different, and is a substituted or unsubstituted C6-30 arylene radical, wherein the bonds are directly connected to an aromatic moiety.
  • Suitable Ar groups in formula (10) can be derived from a C6-30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (3), (4), or (8) above. Combinations comprising at least one of the foregoing dihydroxyarylene compounds can also be used.
  • suitable dihydroxyarylene compounds are l,l-bis(4-hydroxyphenyl) methane, 1,1- bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4- hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l-methylphenyl) propane, l,l-bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulphide), and l,l-bis(4-hydroxy-t-butylphenyl) propane.
  • Combinations comprising at least one of the foregoing dihydroxy compounds can also be used.
  • Units of formula (10) can be derived from the corresponding dihydroxy compound of formula (11):
  • polydiorganosiloxane blocks comprise units of formula (12):
  • R and E are as described above, and each occurrence of R 2 is independently a divalent Ci_3o alkylene, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound.
  • the polydiorganosiloxane blocks are provided by repeating structural units of formula (13):
  • Each R 3 in formula (13) is independently a divalent C2-8 aliphatic group.
  • Each M in formula (13) can be the same or different, and can be a halogen, cyano, nitro, Ci_g alkylthio, Ci_g alkyl, Ci_g alkoxy, C2-8 alkenyl, C2-8 alkenyloxy group, C3-8 cycloalkyl, C3-8 cycloalkoxy, C 6-10 aryl, C 6-10 aryloxy, C 7 . 12 arylalkyl, C 7 _i 2 arylalkoxy, C 7 _i 2 alkylaryl, or C 7 _i 2 alkylaryloxy, wherein each r is independently O, 1, 2, 3, or 4.
  • M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl;
  • R is a dimethylene, trimethylene or tetramethylene group; and
  • R is a Ci_8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R is methyl, or a mixture of methyl and trifluoropropyl, or a mixture of methyl and phenyl.
  • M is methoxy
  • r is one
  • R 3 is a divalent C 1 . 3 aliphatic group
  • R is methyl.
  • Units of formula (13) can be derived from the corresponding dihydroxy polydiorganosiloxane (14):
  • Such dihydroxy polysiloxanes can be made by effecting a platinum catalyzed addition between a siloxane hydride of formula (15):
  • R and E are as previously defined, and an aliphatically unsaturated monohydric phenol.
  • Suitable aliphatically unsaturated monohydric phenols included, for example, eugenol, 2-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl- 4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl- 6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol. Mixtures comprising at least one of the foregoing can also be used.
  • the polysiloxane-polycarbonate can comprise 50 to 99 wt% of carbonate units and 1 to 50 wt% siloxane units. Within this range, the polysiloxane- polycarbonate copolymer can comprise 70 to 98 wt%, specifically 75 to 97 wt% of carbonate units and 2 to 30 wt%, specifically 3 to 25 wt% siloxane units.
  • the polysiloxane-polycarbonate can comprise polysiloxane units, and carbonate units derived from bisphenol A, e.g., the dihydroxy compound of formula (3) in which each of A 1 and A 2 is p-phenylene and Y 1 is isopropylidene.
  • Y 1 is cyclohexylidene.
  • the polysiloxane-polycarbonate comprises polysiloxane units and a carbonate unit derived from l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, or a mixture of unites derived from bisphenol A and l,l-bis(4-hydroxy-3- methy lpheny l)cy clohexane .
  • Polysiloxane-polycarbonates can have a weight average molecular weight of 2,000 to 100,000, specifically 5,000 to 50,000 as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards.
  • the polysiloxane-polycarbonate can have a melt volume flow rate, measured at 300 °C/1.2 kg, of 1 to 50 cubic centimeters per 10 minutes (cc/10 min), specifically 2 to 30 cc/10 min. Mixtures of polysiloxane-polycarbonates of different flow properties can be used to achieve the overall desired flow property.
  • the amount of the polycarbonate component varies with the specific application. In one embodiment, the amount of the polycarbonate component is from 1 to 50 wt%. In another embodiment, the amount of polycarbonate present in the composition ranges from to 5 to 45 wt%. In still another embodiment, the composition comprises 10 to 90 wt% of the polycarbonate component, specifically 20 to 60 wt%, more specifically 20 to 35 wt%, or alternatively 45 to 50 wt%.
  • the polyester component can be any polyester, which when combined with the copolyetheresters and polycarbonate, forms a blend.
  • the polyester component comprises repeating units of the formula (6) as described above.
  • Copolyesters containing a combination of different T and/or D groups can be used.
  • Chemical equivalents of diacids include the corresponding esters, alkyl esters, e.g., Ci_3 dialkyl esters, diaryl esters, anhydrides, salts, acid chlorides, acid bromides, and the like.
  • Chemical equivalents of dihydroxy compounds include the corresponding esters, such as Ci_3 dialkyl esters, diaryl esters, and the like.
  • the polyesters can be branched or linear.
  • Examples of C6-20 aromatic dicarboxylic acids that can be used to prepare the polyesters include isophthalic acid, terephthalic acid, 1 ,2-di(p- carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, and the like, and 1,4- or 1,5 -naphthalene dicarboxylic acids and the like.
  • a combination of isophthalic acid and terephthalic acid can be used, wherein the weight ratio of isophthalic acid to terephthalic acid is 91 :9 to 2:98, specifically 25:75 to 2:98.
  • Exemplary Cs_2o cycloaliphatic dicarboxylic acids contain at least one cycloaliphatic moiety and include monocyclo- and bicyclo- aliphatic acids such as decahydronaphthalene dicarboxylic acids, norbornene dicarboxylic acids, bicyclooctane dicarboxylic acids, 1 ,4-cyclohexanedicarboxylic acid (both cis and trans), specifically trans- 1 ,4-cyclohexanedicarboxylic acid, 1 ,4-hexylenedicarboxylic acid, and the like.
  • Aliphatic C2-20 dicarboxylic acids such as adipic acid, azelaic acid, dicarboxyl dodecanoic acid, and succinic acid can also be useful.
  • Exemplary diols useful in the preparation of the polyesters include aliphatic diols such as ethylene glycol, 1 ,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-l,3-propane diol, 2-ethyl-2-methyl- 1,3 -propane diol, 1,4-butane diol, 1 ,4-but-2-ene diol, 1,3-1,5-pentane diol, 1,5-pentane diol, dipropylene glycol, 2- methyl-l,5-pentane diol, and the like.
  • aliphatic diols such as ethylene glycol, 1 ,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-l,3-propane diol, 2-ethyl-2-methyl- 1,3 -propane diol, 1,4-butane diol, 1 ,4-but-2-ene
  • cycloaliphatic diols include a cycloaliphatic moiety, for example 1,6-hexane diol, dimethanol decalin, dimethanol bicyclooctane, 1 ,4-cyclohexane dimethanol (including its cis- and trans-isomers), triethylene glycol, 1,10-decanediol, and the like.
  • Chemical equivalents of the diols include esters, such as Ci_3 dialkyl esters, diaryl esters, and the like.
  • Specific exemplary poly(alkylene terephthalate) polyesters include poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(ethylene naphthalate) (PEN), poly(butylene naphthalate) (PBN), and poly( 1,3 -propylene terephthalate) (PPT).
  • PET poly(ethylene terephthalate)
  • PBT poly(butylene terephthalate)
  • PEN poly(ethylene naphthalate)
  • PBN poly(butylene naphthalate)
  • PPT poly( 1,3 -propylene terephthalate)
  • the polyester can also include polyesters that contain at least one residue derived from the polyethylene terephthalate component and are selected from (1) modified polybutylene terephthalate random copolymers derived from a polyethylene terephthalate component selected from-the group of polyethylene terephthalate and polyethylene terephthalate copolymers and containing at least one residue derived from the polyethylene terephthalate component and (2) polytrimethylene terephthalate random copolymers that are derived from polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers.
  • the modified polybutylene terephthalate random copolymers can be made by any suitable method in which a polyethylene terephthalate component is depolymerized with a diol and the resulting mixture is polymerized with 1 , 4-butane diol into the modified polybutylene terephthalate random copolymer.
  • the modified polytrimethylene terephthalate random copolymer can be made by any suitable method in which a polyethylene terephthalate component is depolymerized with a diol and the resulting mixture is polymerized with 1 , 3 propane diol into the modified polytrimethylene terephthalate random copolymer.
  • polyesters includes at least one cycloaliphatic moiety. Such polyesters have the formula (16)
  • R 13 and R 14 are independently at each occurrence an aryl, aliphatic or cycloalkane having 2 to 20 carbon atoms and chemical equivalents thereof, with the proviso that at least one of R 13 and R 14 is a cycloaliphatic group.
  • the cycloaliphatic polyester is a condensation product where R 13 is the residue of a diol or a chemical equivalent thereof and R 14 is decarboxylated residue of a diacid or a chemical equivalent thereof.
  • cycloaliphatic polyesters are those having both R 13 and R 14 as cycloalkyl containing radicals. Such polyesters generally contain at least 50 mole % of cycloaliphatic diacid and/or cycloaliphatic diol components, the remainder, if any, being linear aliphatic diacids and/or diols.
  • R 13 and R 14 are cycloalkyl radicals independently selected from the following structural units of (17).
  • the diol or chemical equivalent thereof used is 1,4- cyclohexane dimethanol or a chemical equivalent thereof. Either or both of the cis or trans isomers of the 1 ,4-cyclohexane dimethanol can be used.
  • Chemical equivalents to the diols include esters, such as dialkylesters, diaryl esters, and the like. Specific non-limiting examples of diacids include decahydro naphthalene dicarboxylic acids, norbornene dicarboxylic acids, bicyclo octane dicarboxylic acids, 1,4- cyclohexanedicarboxylic acid or the chemical equivalents thereof.
  • the diacids include trans- 1 ,4-cyclohexanedicarboxylic acid or a chemical equivalent thereof.
  • Chemical equivalents of these diacids include esters, alkyl esters, e.g., dialkyl esters, diaryl esters, anhydrides, salts, acid chlorides, acid bromides, and the like.
  • the chemical equivalent comprises the dialkyl esters of the cycloaliphatic diacids, and most specifically the chemical equivalent comprises the dimethyl ester of the acid, such as dimethyl- 1,4-cyclohexane-dicarboxylate.
  • Cyclohexane dicarboxylic acids and their chemical equivalents can be prepared, for example, by the hydrogenation of cycloaromatic diacids and corresponding derivatives such as isophthalic acid, terephthalic acid or naphthalenic acid in a suitable solvent such as water or acetic acid using a suitable catalysts such as rhodium supported on a carrier such as carbon or alumina. They can also be prepared by the use of an inert liquid medium in which a phthalic acid is at least partially soluble under reaction conditions and with a catalyst of palladium or ruthenium on carbon or silica.
  • cis- and trans-isomers typically, in the hydro genation, two isomers are obtained in which the carboxylic acid groups are in cis- or trans-positions.
  • the cis- and trans-isomers can be separated by crystallization with or without a solvent, for example, using n- heptane, or by distillation.
  • the cis- and trans- isomers have different physical properties and can be used independently or as a mixture. Mixtures of the cis- and trans-isomers are useful herein as well.
  • a copolyester or a mixture of two polyesters can be used as the cycloaliphatic polyester.
  • the cycloaliphatic radical R 14 is derived from the 1 ,4-cyclohexyl diacids with generally greater than 70 mole % thereof in the form of the trans isomer
  • the cycloaliphatic radical R 13 is derived from a 1 ,4-cyclohexyl diols such as 1 ,4-cyclohexyl dimethanol, with greater than 70 mole % thereof in the form of the trans isomer.
  • a specific cycloaliphatic polyester is poly(cyclohexane-l,4- dimethylene cyclohexane-l,4-dicarboxylate) also referred to as poly(l,4-cyclohexane- dimethanol-l,4-dicarboxylate) (PCCD).
  • ester is poly(l,4- cyclohexylene dimethylene co-ethylene terephthalate) (PCTG) wherein greater than 50 mol% of the ester groups are derived from 1 ,4-cyclohexanedimethanol; and poly(ethylene-co-l,4-cyclohexylenedimethylene terephthalate) wherein greater than 50 mol% of the ester groups are derived from ethylene (PTCG).
  • PCTG poly(l,4- cyclohexylene dimethylene co-ethylene terephthalate)
  • PTCG poly(ethylene-co-l,4-cyclohexylenedimethylene terephthalate)
  • PTCG ethylene
  • any of the above polyesters with minor amounts, e.g., from 0.5 to 5 percent by weight, of units derived from aliphatic acid and/or aliphatic polyols to form copolyesters.
  • the aliphatic polyols include glycols, such as poly(ethylene glycol) or poly(butylene glycol).
  • glycols such as poly(ethylene glycol) or poly(butylene glycol).
  • Such polyesters can be made following the teachings of, for example, U.S. Pat. Nos. 2,465,319 and 3,047,539.
  • the cycloaliphatic polyesters have a weight-average molecular weight (Mw), measured, for example, by ultra-centrifugation or light scattering of 25,000 Daltons to 85,000 Daltons.
  • Mw weight-average molecular weight
  • the weight average molecular weight is more specifically 30,000 Daltons to 80,000 Daltons and most specifically 60,000 to 80,000 Daltons.
  • the amount of the polyester component varies with the specific application. In one embodiment, the amount of the polyester component is from more than 0 to 60 wt%. In another embodiment, the amount of polyester present in the composition ranges from to 1 to 50 wt%. In still another embodiment, the composition comprises 10 to 80 wt% of the polyester component, specifically 20 to 60 wt%, more specifically 40 to 55 wt%.
  • the blends can contain additives, e.g., carboxy reactive components and flame retardants.
  • the flame-retarding component can be added the composition to suppress, reduce, delay, or modify the propagation of a flame through a composition or an article based on the composition.
  • the flame -retarding component can be halogenated hydrocarbons (chlorine and bromine containing compounds and reactive flame retardants), inorganic flame retardants (boron compounds, antimony oxides, aluminum hydroxide, molybdenum compounds, zinc and magnesium oxides), phosphorous containing compounds (organic phosphate esters, phosphates, halogenated phosphorus compounds and inorganic phosphorus containing salts) and nitrogen containing compounds like melamine cyanurate.
  • Inorganic flame retardants can include metal hydroxides, antimony compounds, boron compounds, other metal compounds, phosphorous compounds, and other inorganic flame retardant compounds.
  • suitable metal hydroxides include magnesium hydroxide, aluminum hydroxide, and other metal hydroxides.
  • suitable antimony-based flame retardants include antimony trioxide, sodium antimonate, antimony pentoxide, and other antimony-based inorganic compounds.
  • suitable boron compounds include zinc borate, boric acid, borax, as well as other boron-based inorganic compounds.
  • metal compounds examples include molybdenum compounds, molybdenum trioxide, ammonium octamolybdate (AOM), zirconium compounds, titanium compounds, zinc compounds such as zinc stannate, zinc hydroxy-stannate, mono zinc phosphate, as well as others.
  • the flame retarding component can be added the composition to suppress, reduce, delay, or modify the propagation of a flame through a composition or an article based on the composition.
  • the flame retarding component can be halogenated hydrocarbons (chlorine and bromine containing compounds and reactive flame retardants), inorganic flame retardants (boron compounds, antimony oxides, aluminum hydroxide, molybdenum compounds, zinc and magnesium oxides), phosphorous containing compounds (organic phosphates, phosphinates, phosphites, phosphonates, phosphines, halogenated phosphorus compounds and inorganic phosphorus containing salts) and nitrogen containing compounds like melamine cyanurate.
  • Inorganic flame retardants can include metal hydroxides, antimony compounds, boron compounds, other metal compounds, phosphorous compounds, and other inorganic flame-retarding compounds.
  • suitable metal hydroxides include magnesium hydroxide, aluminum hydroxide, and other metal hydroxides.
  • suitable antimony-based flame retardants include antimony trioxide, sodium antimonate, antimony pentoxide, and other antimony-based inorganic compounds.
  • suitable boron compounds include zinc borate, boric acid, borax, as well as other boron-based inorganic compounds.
  • metal compounds examples include molybdenum compounds, molybdenum trioxide, ammonium octamolybdate (AOM), zirconium compounds, titanium compounds, zinc compounds such as zinc stannate, zinc hydroxy-stannate, mono zinc phosphate, as well as others.
  • the flame retarding component can include halogen-containing compounds.
  • suitable halogenated organic flame retardants can include brominated flame retardants and chlorinated flame retardants.
  • flame retardants include tetrabromobisphenol A, octabromobiphenyl ether, decabromodiphenyl ether, bis(tribromophenoxy) ethane, tetrabromobiphenyl ether, hexabromocyclododecane, tribromophenol, bis(tribromophenoxy) ethane tetrabromobisphenol A polycarbonate oligomers, and tetrabromobisphenol A epoxy oligomers.
  • halogenated aromatic flame-retardants include tetrabromobisphenol A polycarbonate oligomer, polybromophenyl ether, brominated polystyrene, brominated BPA polyepoxide, brominated imides, brominated polycarbonate, poly (haloaryl acrylate), poly (haloaryl methacrylate), or mixtures thereof.
  • Examples of other suitable flame retardants are brominated polystyrenes such as polydibromostyrene and polytribromostyrene, decabromobiphenyl ethane, tetrabromobiphenyl, brominated alpha, omega-alkylene- bis-phthalimides, e.g. N,N'-ethylene- bis-tetrabromophthalimide, oligomeric brominated carbonates, especially carbonates derived from tetrabromobisphenol A, which, if desired, are end- capped with phenoxy radicals, or with brominated phenoxy radicals, or brominated epoxy resins.
  • brominated polystyrenes such as polydibromostyrene and polytribromostyrene, decabromobiphenyl ethane, tetrabromobiphenyl, brominated alpha, omega-alkylene- bis-phthalimides, e.g. N,N'-ethylene- bis-tetrab
  • Chlorinated flame retardants include chlorinated paraffins, bis (hexachlorocyclopentadieno)cyclo-octane as well other such functionally equivalent materials.
  • the flame retarding component can include phosphorus-containing compounds.
  • suitable phosphorous flame retardants include red phosphorus, ammonium polyphosphate.
  • Organophosphor o us flame retardants can include halogenated phosphates, non-halogenated compounds.. Examples of such materials include tris(l-chloro- 2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2,3-dibromopropyl) phosphate, phosphate esters, trialkyl phosphates, triaryl phosphates, aryl-alkyl phosphates, and combinations thereof.
  • Other flame retardants can include polyols, phosphonium derivatives, phosphonates, phosphanes, and phosphines.
  • Specific phosphorous-containing compounds include phosphates of the formula:
  • RO-P-OR I OR wherein each R is independently a C 1-18 alkyl, cycloalkyl, aryl, or arylalkyl, e.g., cyclohexyl, isopropyl, isobutyl, and the like; phosphonates of the formula:
  • I Y wherein X and Y is H, and R is a C 1-18 alkyl, cycloalkyl, aryl, or arylalkyl, e.g., cyclohexyl, isopropyl, isobutyl, and the like; phosphine oxides of the formula: o
  • I Y wherein X, Y, and Z are H and R, is a C 1-18 alkyl, cycloalkyl, aryl, arylalkyl, e.g., cyclohexyl, isopropyl, isobutyl, and the like; phosphines of the formula: z— p— x
  • X, Y, and Z is each independently a H, C 1-18 alkyl, cycloalkyl, aryl, arylalkyl, and the like; or a phosphite of the formula:
  • RO- P— OR I OR wherein each R is independently the same or different can be selected from the group Of C 1-18 alkyl, cycloalkyl, aryl, or arylalkyl, e.g., cyclohexyl, isopropyl, isobutyl, and the like, and H.
  • suitable flame retarding agents may be organic compounds that include phosphorus, bromine, and/or chlorine.
  • Non- brominated and non-chlorinated phosphorus-containing flame retardants may be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus-nitrogen bonds.
  • Two of the G groups may be joined together to provide a cyclic group, for example, diphenyl pentaerythritol diphosphate, which is described by Axelrod in U.S. Pat. No. 4,154,775.
  • aromatic phosphates may be, for example, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'- trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate,
  • a specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.
  • Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of the formulas below:
  • suitable di- or polyfunctional aromatic phosphorus- containing compounds include resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol-A, respectively, their oligomeric and polymeric counterparts, and the like.
  • exemplary suitable flame retarding compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl) phosphine oxide.
  • phosphorus-containing flame retardants are generally present in amounts of about 1 to about 20 parts by weight, based on 100 parts by weight of the total resin in the final composition.
  • the flame retarding polyester composition includes a flame retarding quantity of one or a mixture of nitrogen-containing flame retardants such as triazines, guanidines, cyanurates, and isocyanurates.
  • nitrogen-containing flame retardants such as triazines, guanidines, cyanurates, and isocyanurates.
  • Suitable triazines have the formula
  • R 1 , R 2 , and R 3 are independently C 1-12 alkyl, C 1-12 alkoxyl, C ⁇ -u aryl, amino, C 1-12 alkyl-substituted amino, or hydrogen.
  • Highly suitable triazines include 2,4,6- triamine-1,3, 5-triazine (melamine, CAS Reg. No. 108-78-1), melamine derivatives, melam, melem, melon, ammeline (CAS Reg. No. 645-92- 1), ammelide (CAS Reg. No. 645-93-2), 2-ureidomelamine, acetoguanamine (CAS Reg. No. 542-02-9), benzoguanamine (CAS Reg. No. 91-76-9), and the like.
  • Salts/adducts of these compounds with boric acid or phosphoric acid may be used in the composition.
  • examples include melamine pyrophosphate and melamine polyphosphate.
  • Suitable cyanurate/isocyanurate compounds include salts/adducts of the triazine compounds with cyanuric acid, such as melamine cyanurate and any mixtures of melamine salts.
  • Suitable guanidine compounds include guanidine; aminoguanidine; and the like; and their salts and adducts with boric acid, carbonic acid, phosphoric acid, nitric acid, sulfuric acid, and the like; and mixtures comprising at least one of the foregoing guanidine compounds.
  • the nitrogen-containing flame retardants are often used in combination with one or more phosphorous-based compounds, for example the phosphinates and diphosphinates set forth in U.S. Pat. No. 6,255,371 to Schosser et al.
  • Specific phosphinates include aluminum diethylphosphinate (DEPAL), and zinc diethylphosphinate (DEPZN).
  • DEPAL aluminum diethylphosphinate
  • DEPZN zinc diethylphosphinate
  • the phosphinates have the formula (18)
  • Ri and R 2 are the same or different, and are H, Ci_6 alkyl (linear or branched), and/or aryl; R3 is Ci_io alkylene, (linear or branched), C ⁇ -io arylene, C ⁇ -io alkylarylene or C ⁇ -io arylalkylene; M is any metal, e.g., magnesium, calcium, aluminum or zinc, m is 1, 2 or 3; n is 1, 2 or 3; and x is 1 or 2.
  • Ri and R 2 can be H. This results in a hypophosphite, a subset of phosphinate, such as calcium hypophosphite, aluminum hypophosphite, and the like.
  • the flame retardants are typically used with a synergist, particularly inorganic antimony compounds.
  • Typical inorganic synergist compounds include Sb 2 Os, SbS 3 , sodium antimonate, and the like.
  • Especially suitable is antimony trioxide (Sb 2 O 3 ).
  • Synergists such as antimony oxides are typically used in an amount of about 0.5 to 15 % by weight, based on the weight of resin in the final composition.
  • the present composition may contain polytetrafluoroethylene (PTFE) type resins or copolymers, which are used either to reduce dripping in flame retardant thermoplastics or to form fibrillar network in the composition.
  • PTFE polytetrafluoroethylene
  • the fluoropolymer is at least partially encapsulated by an encapsulating thermoplastic polymer, for example PTFE/SAN, synthesized by aqueous emulsion polymerization as disclosed in U.S. Patent No. 5,804,654.
  • Flame retardant additives are desirably present in an amount at least sufficient to reduce the flammability of the polyester resin, preferably to a UL94 V-O rating.
  • the amount will vary with the nature of the resin and with the efficiency of the additive.
  • the amount of the flame retarding component is generally at least 1 wt%, based on the weight of resin in the final composition. In one embodiment, the amount of the flame retarding component is from 5 wt% to 30 wt%, based on the weight of resin in the final composition. In another embodiment, the amount of the flame retarding component is from 0.01 to 20 wt%, or from 10 to 20 wt%, based on the weight of polymer in the final composition.
  • the carboxy-reactive material is a mono functional or a polyfunctional carboxy-reactive material that can be either polymeric or non-polymeric.
  • carboxy-reactive groups include epoxides, carbodiimides, orthoesters, oxazolines, oxiranes, aziridines, and anhydrides.
  • the carboxy-reactive material can also include other functionalities that are either reactive or non-reactive under the described processing conditions.
  • Non- limiting examples of reactive moieties include reactive silicon-containing materials, for example epoxy-modified silicone and silane monomers and polymers.
  • a catalyst or co-catalyst system can be used to accelerate the reaction between the carboxy-reactive material and the polyester.
  • polyfunctional or “multifunctional” in connection with the carboxy-reactive material means that at least two carboxy-reactive groups are present in each molecule of the material.
  • Particularly useful polyfunctional carboxy-reactive materials include materials with at least two reactive epoxy groups.
  • the polyfunctional epoxy material can contain aromatic and/or aliphatic residues.
  • Examples include epoxy novolac resins, epoxidized vegetable (e.g., soybean, linseed) oils, tetraphenylethylene epoxide, styrene-acrylic copolymers containing pendant glycidyl groups, glycidyl methacrylate-containing polymers and copolymers, and difunctional epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate .
  • epoxidized vegetable e.g., soybean, linseed
  • tetraphenylethylene epoxide tetraphenylethylene epoxide
  • styrene-acrylic copolymers containing pendant glycidyl groups glycidyl methacrylate-containing polymers and copolymers
  • difunctional epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxy
  • the polyfunctional carboxy-reactive material is an epoxy- functional polymer, which as used herein include oligomers.
  • Exemplary polymers having multiple epoxy groups include the reaction products of one or more ethylenically unsaturated compounds (e.g., styrene, ethylene and the like) with an epoxy-containing ethylenically unsaturated monomer (e.g., a glycidyl Ci_ 4 (alkyl)acrylate, allyl glycidyl ethacrylate, and glycidyl itoconate).
  • ethylenically unsaturated compounds e.g., styrene, ethylene and the like
  • an epoxy-containing ethylenically unsaturated monomer e.g., a glycidyl Ci_ 4 (alkyl)acrylate, allyl glycidyl ethacrylate, and glycidyl itoconate.
  • the polyfunctional carboxy-reactive material is a styrene-acrylic copolymer (including an oligomer) containing glycidyl groups incorporated as side chains.
  • a styrene-acrylic copolymer including an oligomer
  • glycidyl groups incorporated as side chains are described in the International Patent Application WO 03/066704 Al, assigned to Johnson Polymer, LLC, which is incorporated herein by reference in its entirety. These materials are based on copolymers with styrene and acrylate building blocks that have glycidyl groups incorporated as side chains.
  • a high number of epoxy groups per polymer chain is desired, at least about 10, for example, or greater than about 15, or greater than about 20.
  • These polymeric materials generally have a molecular weight greater than about 3000, preferably greater than about 4000, and more preferably greater than about 6000. These are commercially available from BASF under the Joncryl® trade name, preferably the Joncryl® ADR 4368 material.
  • a carboxy-reactive copolymer is the reaction product of an epoxy- functional Ci_ 4 (alkyl)acrylic monomer with a non- functional styrenic and/or Ci_ 4 (alkyl)acrylate and/or olefin monomer.
  • the epoxy polymer is the reaction product of an epoxy- functional (meth)acrylic monomer and a non- functional styrenic and/or (meth)acrylate monomer.
  • carboxy reactive materials are characterized by relatively low molecular weights.
  • the carboxy reactive material is an epoxy-functional styrene (meth)acrylic copolymer produced from an epoxy functional (meth)acrylic monomer and styrene.
  • (meth)acrylic includes both acrylic and methacrylic monomers
  • (meth)acrylate includes both acrylate and methacrylate monomers.
  • specific epoxy- functional (meth)acrylic monomers include, but are not limited to, those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate.
  • Suitable Ci_ 4 (alkyl)acrylate comonomers include, but are not limited to, acrylate and methacrylate monomers such as methyl acrylate, ethyl acrylate, n- propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t- butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate,
  • Suitable styrenic monomers include, but are not limited to, styrene, alpha-methyl styrene, vinyl toluene, p-methyl styrene, t-butyl styrene, o- chlorostyrene, and mixtures comprising at least one of the foregoing.
  • the styrenic monomer is styrene and/or alpha-methyl styrene.
  • the carboxy reactive material is an epoxy compound having two terminal epoxy functionalities, and optionally additional epoxy (or other) functionalities.
  • the compound can further contain only carbon, hydrogen, and oxygen.
  • Difunctional epoxy compounds, in particular those containing only carbon, hydrogen, and oxygen can have a molecular weight of below about 1000 g/mol, to facilitate blending with the polyester resin.
  • the difunctional epoxy compounds have at least one of the epoxide groups on a cyclohexane ring.
  • Exemplary difunctional epoxy compounds include, but are not limited to, 3, 4-epoxycyclohexyl-3,4-epoxy cyclohexyl carboxylate, bis(3,4- epoxycyclohexylmethyl) adipate, vinylcyclohexene di-epoxide, bisphenol diglycidyl ethers such as bisphenol-A diglycidyl ether, tetrabromobisphenol-A diglycidyl ether, glycidol, diglycidyl adducts of amines and amides, diglycidyl adducts of carboxylic acids such as the diglycidyl ester of phthalic acid the diglycidyl ester of hexahydrophthalic acid, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, butadiene diepoxide, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and the
  • the difunctional epoxide compounds can be made by techniques well known to those skilled in the art.
  • the corresponding ⁇ - or ⁇ -dihydroxy compounds can be dehydrated to produce the epoxide groups, or the corresponding unsaturated compounds can be epoxidized by treatment with a peracid, such as peracetic acid, in well-known techniques.
  • a peracid such as peracetic acid
  • epoxy-functional materials are available from Dow Chemical Company under the tradename D.E.R.332, D.E.R.661, and D.E.R.667; from Resolution Performance Products under the trade name EPON Resin 100 IF, 1004F, 1005F, 1007F, and 1009F; from Shell Oil Corporation under the trade names EPON 826, 828, and 871; from Ciba-Giegy Corporation under the trade names CY-182 and CY-183; and from Dow Chemical Co. under the tradename ERL-4221 and ERL- 4299.
  • BASF is a supplier of an epoxy functionalized material known as ADR4368 and 4300.
  • a further example of a polyfunctional carboxy-reactive material is a co- or terpolymer including units of ethylene and glycidyl methacrylate (GMA), sold by Arkema under the trade name LOTADER ® .
  • the carboxy-reactive material is a multifunctional material having two or more reactive groups, wherein at least one of the groups is an epoxy group and at least one of the groups is a group reactive with the polyester, but is not an epoxy group.
  • the second reactive group can be a hydroxyl, an isocyanate, a silane, and the like.
  • Examples of such multifunctional carboxy-reactive materials include materials with a combination of epoxy and silane functional groups, preferably terminal epoxy and silane groups.
  • the epoxy silane is generally any kind of epoxy silane wherein the epoxy is at one end of the molecule and attached to a cycloaliphatic group and the silane is at the other end of the molecule.
  • a desired epoxy silane within that general description is of the following formula:
  • s is an integer of 1, 2 or 3
  • t is an integer of 1 to 6, inclusive
  • J, K, and L are the same or different, preferably the same, and are alkyl groups of one to twenty carbon atoms, inclusive, cycloalkyl of four to ten carbon atoms, inclusive, alkylene phenyl wherein alkylene is one to ten carbon atoms, inclusive, and phenylene alkyl wherein alkyl is one to six carbon atoms, inclusive.
  • Desirable epoxy silanes within this range are compounds wherein s is 2, t is 1 or 2, desirably 2, and J, K, and L are the same and are alkyl of 1, 2, or 3 carbon atoms inclusive.
  • Epoxy silanes within the range which in particular can be used are those wherein s is 2, t is 2, and J, K, and L are the same and are methyl or ethyl.
  • Such materials include, for example, ⁇ -(3,4-epoxycyclohexyl) ethyltriethoxysilane, available under the trade name CoatOSil 1770 from Momentive Performance Materials, Inc.
  • Other examples are ⁇ -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, available under the trade name Silquest A-186 from Momentive Performance Materials, Inc, and 3-glycidoxypropyltriethoxysilane, available under the trade name Silquest Y-15589 from Momentive Performance Materials, Inc.
  • the carboxy-reactive material is added to the polyester compositions in amounts effective to improve visual and/or measured physical properties.
  • the carboxy-reactive materials are added to the polyester compositions in an amount effective to improve the solvent resistance of the composition, in particular the fuel-resistance of the composition.
  • a person skilled in the art can determine the optimum type and amount of any given carboxy-reactive material without undue experimentation, using the guidelines provided herein.
  • the type and amount of the carboxy reactive material will depend on the desired characteristics of the composition, the type of polyester used, the type and amount of other additives present in the composition and like considerations, and is generally at least 0.01 wt% based on the weight of the total composition. In one embodiment, the amount of the carboxy-reactive material is 0.01 to 30 wt%, or more, specifically 0.01 to 20 wt%, 1 to 10 wt%, more specifically 1 to 5 wt%, based on the total polymer.
  • the blends are made by combining suitable amounts of the copolyetheresters and the polycarbonate.
  • the process involves making a copolyetherester by either process described above and further adding a polycarbonate in sufficient amounts to form the blend.
  • the ingredients can be tumble -blended and then compounded on a twin screw extruder with vacuum vented co-rotating mixing screws.
  • the temperature can be set at a suitable temperature, e.g., from 200 to 25O 0 C and screw speed between a setting such as 400 and 450 rpm.
  • the extrudate is cooled through a water bath prior to pelletization.
  • the typical output rate for the extruder is about 50 lbs/hr (approximately 127 kg/hour). Other outputs are possible.
  • compositions can be molded or extruded to form an article.
  • a method of forming an article comprises shaping, extruding, blow molding, or injection molding any of the compositions encompassed by the invention.
  • the articles are transparent.
  • the process for making the elastomer blends can advantageously substantially reduce carbon dioxide emissions and solid waste. Since the elastomer blends are made from scrap PET and not monomers, the process significantly reduces the amount of carbon dioxide emissions and solid waste. Carbon waste reduction (or crude oil savings) occurs because the carbon that constitutes the dimethyl terephthalate or terephthalic acid ordinarily used to make polyesters is substituted by a scrap PET component, e.g., polyester scrap.
  • the process to make DMT or TPA from crude oil is highly energy intensive and as a result, substantial emissions of carbon dioxide (CO 2 ) to the atmosphere occurs from burning of non-renewable energy sources.
  • the process for making PET-derived modified PBT can eliminate at least 1 kg of CO 2 emissions for every kilogram of PET-derived modified PBT made with the process, as compared to a process that makes virgin PBT homopolymers from monomers. In another embodiment, the process for making PET-derived modified PBT can eliminate from 1 kg to 1.5 kg, or more CO 2 emissions for every kilogram of PET-derived modified PBT made with the inventive process, as compared to a process that makes virgin PBT homopolymers from monomers. Additionally, there are energy savings and reduced carbon dioxide emissions when the ethylene glycol byproduct is recovered and is used instead of ordinary ethylene glycol in manufacturing.
  • biomass-derived feedstocks such as succinic acid
  • the carbon dioxide savings are further increased for two reasons.
  • Biomass-derived succinic acid is made form sugars or other biomass- derived hydrocarbons that are derived from atmospheric carbon rather than fossil fuel carbon sources, thus reducing the environmental impact of the polymer derived from BDO using succinic acid from biomass sources.
  • the fermentation to yield succinic acid requires carbon dioxide as an input thus leading to further carbon dioxide reductions.
  • modified polybutylene terephthalate random copolymers can have a reduced CO 2 emissions index.
  • the reduced CO 2 emissions index is the amount of CO 2 , expressed in kilogram (kg), that is saved when one (1) kg of a composition containing the modified polybutylene terephthalate random copolymers is made, as compared to the amount of CO 2 , expressed in kg, that is created when the composition is made with polybutylene terephthalate that is derived from monomers.
  • the modified PBT random copolymers have a reduced CO 2 emissions index that is more than approximately 1.3 kg, and can range from 1.3 kg to 2.5 kg.
  • the difference between the amount of CO2 that is created during ordinary processes for making virgin, monomer-derived PBT and the process for making 1 kg of the modified polybutylene terephthalate random copolymers can range from 1.3 kg to 2.5 kg, or more particularly from 1.7 kg to 2.2 kg. This difference is based on calculations for the entire process that starts from crude oil to the monomers to the PBT, versus the process of converting scrap PET to oligomers to the modified PBT. In other words, the process for making 1 kg of the modified polybutylene terephthalate random copolymers creates 1.3 to 2.5 kilograms less CO 2 as compared to the process for making 1 kg of virgin PBT from crude oil.
  • thermoplastic poly ether-ester (TPEE) elastomers experimental materials "TPEE-I” and “TPEE-2,” was an elastomer containing a modified, random polybutylene terephthalate copolymer block that was derived from a polyethylene terephthalate component and that comprises a residue derived from the polyethylene terephthalate component; and a polyalkylene oxide copolymer block that was derived from a polyethylene terephthalate component and a polyalkylene oxide glycol, and that contains polyalkylene oxide groups and a residue derived from the polyethylene terephthalate component. Both elastomers were derived from post consumer polyethylene terephthalate (PET)
  • Table 1 shows intrinsic viscosity (IV), the melt temperature of the polyester component, Tm, in degrees Centigrade ( 0 C), and the glass transition temperature of the polyester component, Tg, in 0 C, as measured by DSC. Table 1 also shows the composition as measured by NMR (see section Testing Protocols/Techniques/ Procedures).
  • PTHF stands for poly(oxytetramethylene)glycol, which constitutes the so-called soft blocks in these elastomers.
  • Polycarbonates LEXAN® 101 polycarbonate; polycarbonate comprising 50 weight percent l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC); polysiloxane-polycarbonate, all from General Electric.
  • DMBPC l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane
  • Polyester poly l,4-cyclohexylenedimethylene-l,4- cyclohexanedicarboxylate (PCCD) with an IV between 0.92 and 1.02, from Eastman Chemical Company.
  • compositions were prepared with the ingredients tumble-blended and then compounded on a 27 mm Werner Pfleiderer Twin Screw Extruder with vacuum vented co-rotating mixing screws.
  • the temperature was set at 200 0 C to 25O 0 C and screw speed between 400 and 450 revolutions per minute (rpm).
  • the extrudate was cooled through a water bath prior to pelletization.
  • the typical output rate for this extruder was about 50 lbs/hr (23 kg/hr).
  • Haze and total luminous transmittance (%) were each measured on ASTM D 1003-00. The following classification is used as a guideline for samples of 3.2 mm thickness: Transmission greater than 60% is classified as transparent, Transmission greater than or equal to 35% is classified as translucent, and Transmission less than 35% is classified as opaque.
  • VST Vicat softening temperature
  • Melt volume flow ratio was measured at the indicated temperature (25O 0 C) under a load of 1.20 Kg in accordance with ISO 1133. MVR is reported in cubic centimeters per 10 minutes (cm 3 /10 min).
  • Flexural modulus is based on the ASTM D790 method. Typical articles used were injection molded articles. More specifically, injection molded test bars had the following dimensions: 1/8 inch (3.175 mm) x 1 A inch x 5 inches (127 mm) . The final test results were calculated as the average of test results of five test bars. The flexural modulus is the ratio, within the elastic limit, of stress to corresponding strain and is expressed in Megapascals (MPa).
  • Izod impact strength was measured at room temperature according to ASTM D 256 using molded bars having dimensions of 1/8 inch (3.175 mm) x Vi inch (12.7 mm) x 2-1/2 inches (63.5 mm). The results of the test are reported in terms of energy absorbed per unit specimen width, expressed in Joule/m (J/m). Typically the final test result was calculated as the average of test results of five test bars.
  • Tensile performance data were measured according to ASTM D638 for Low-Modulus materials. This test method was used to determine the tensile properties of low-modulus plastic, ASTM Type I, injection molded articles (dumbbell-shaped bars). The test had an initial speed of one inch (2.54 cm) per minute and after 50% strain increases to two inches per minute. The test ran until the sample breaks or until the extensometer reached its extension limit of 400%. Tensile Modulus, Stress at 5% Strain, Stress at 10% Strain, Stress at 50% Strain, Stress at Maximum Strain, and Nominal Strain at Break are reported.
  • Multi-axial impact performance data were measured according to ASTM D3763 at 0 and 23 0 C. The test provides information on how a material behaved under multiaxial deformation conditions. The deformation applied was a high-speed puncture. Results are expressed in Joules as total impact energy.
  • Example 2 The results for Examples 1-2 are shown in Table 2. More specifically, the examples were blends containing an elastomer that included a modified, random polybutylene terephthalate copolymer block that was derived the polyethylene terephthalate component and that comprises a residue derived from the polyethylene terephthalate component; and a polyalkylene oxide copolymer block that was derived from the polyethylene terephthalate component and a polyalkylene oxide glycol, and that contained polyalkylene oxide groups and a residue derived from the polyethylene terephthalate component.
  • compositions and properties of Examples 3 and 4 of the invention comprised PET derived elastomers and PC copolymer, specifically DMBPC.
  • compositions of Examples 5 and 6 were both classified as opaque based on the transmission data (66 and 76%, respectively). The results also indicate that the compositions exhibited useful performance properties.
  • compositions of Examples 1 and 2 were both classified as transparent, with a transmission of 66%. The results also indicated that the compositions exhibited useful performance properties.
  • compositions include PET derived elastomers and polysiloxane- polycarbonate copolymers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne une composition comprenant de 10 à 90 % en poids d'un élastomère de copolyétherester, qui comprend : un bloc de copolymère de téréphtalate de polybutylène statistique modifié qui est dérivé d'un composant téréphtalate de polyéthylène choisi dans le groupe constitué par le téréphtalate de polyéthylène, les copolymères de téréphtalate de polyéthylène, et les combinaisons de ceux-ci ; et qui contient au moins un résidu dérivé du composant téréphtalate de polyéthylène ; et un bloc de copolymère d'oxyde de polyalkylène qui est dérivé du composant téréphtalate de polyéthylène et un glycol d'oxyde de polyalkylène, et qui contient un oxyde de polyalkylène et au moins un résidu dérivé du composant téréphtalate de polyéthylène ; de 10 à 90 % en poids d'un polycarbonate ; et de 0 à 60 % en poids d'un polyester.
PCT/US2007/074242 2006-07-26 2007-07-24 Mélange d'élastomère contenant des polycarbonates et des copolyétheresters dérivés de téréphtalate de polyéthylène, procédé de fabrication, et articles formés à partir de ceux-ci Ceased WO2008014273A1 (fr)

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US8034870B2 (en) 2003-12-17 2011-10-11 Sabic Innovative Plastics Ip B.V. Flame-retardant polyester composition
US8188172B2 (en) 2003-12-17 2012-05-29 Sabic Innovative Plastics Ip B.V. Polyester compositions, method of manufacture, and uses thereof
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WO2010078141A3 (fr) * 2008-12-30 2010-08-26 Sabic Innovative Plastics Ip B.V. Procédé de fabrication de copolymères de polycyclohexane diméthylène téréphtalate à partir de poly(téréphtalate d'éthylène) et compositions et articles à base de ces copolymères
US7829614B2 (en) 2008-12-30 2010-11-09 Sabic Innovative Plastics Ip B.V. Reinforced polyester compositions, methods of manufacture, and articles thereof
US8138244B2 (en) 2008-12-30 2012-03-20 Sabic Innovative Plastics Ip B.V. Reinforced polyester compositions, method of manufacture, and articles thereof
EP2447298A1 (fr) * 2008-12-30 2012-05-02 SABIC Innovative Plastics B.V. Procédé de fabrication de copolymères de polycyclohéxane, diméthylène, téréphthalate à partir de téréphthalate de polyéthylène et compositions et articles correspondants
US8686072B2 (en) 2010-06-29 2014-04-01 Sabic Innovative Plastics Ip B.V. Flame resistant polyester compositions, method of manufacture, and articles therof
US8716378B2 (en) 2010-06-29 2014-05-06 Sabic Innovative Plastics Ip B.V. Flame resistant polyester compositions, method of manufacture, and articles thereof
US9441106B2 (en) 2011-11-11 2016-09-13 Sabic Global Technologies B.V. Composition, multilayer sheets made therefrom, and methods for making and using the same

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EP2044151A1 (fr) 2009-04-08
US8309656B2 (en) 2012-11-13
US20130012666A1 (en) 2013-01-10
US20080027167A1 (en) 2008-01-31

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